JPS58132058A - Electrically conductive paint composition - Google Patents
Electrically conductive paint compositionInfo
- Publication number
- JPS58132058A JPS58132058A JP57013960A JP1396082A JPS58132058A JP S58132058 A JPS58132058 A JP S58132058A JP 57013960 A JP57013960 A JP 57013960A JP 1396082 A JP1396082 A JP 1396082A JP S58132058 A JPS58132058 A JP S58132058A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- viscosity
- dispersion
- solvent
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
Abstract
Description
【発明の詳細な説明】 本発明は、導電性塗料組成物に関する。[Detailed description of the invention] The present invention relates to conductive coating compositions.
導電性カーボンブラックまたはカーボンブラッりとグラ
ファイトを溶剤型高分子材料と共に溶剤に均一分散させ
た導電性塗料は、優れた電気特性を有するため、各種電
気部品材料、建築材料などとして各分野番こおいて広く
使用されている。Conductive paint, which is made by uniformly dispersing conductive carbon black or graphite in a solvent together with a solvent-based polymer material, has excellent electrical properties and is therefore popular in various fields as a material for various electrical parts and as a building material. It is widely used.
通常この導電性塗料は、カーボンブラックまたはグラフ
ァイト粉末と高分子材料を有機溶剤と共に均一に混線し
て調製されている。しかし、塗料ベースである高分子溶
液中にカーボンブラックまたはグラファイトを均一かつ
安定に分散させることは、各成分の比重、粒度、流動性
が異なるため、かなり困難であり、所定の抵抗値の塗膜
を再現性よく得ることは難かしい。また、分散が不均一
であると、カーボンブラックなどの混入量を多くしても
、その割に体積抵抗率を低くすることができないという
難点もある。Usually, this conductive paint is prepared by uniformly mixing carbon black or graphite powder and a polymeric material with an organic solvent. However, it is quite difficult to uniformly and stably disperse carbon black or graphite in the polymer solution that is the paint base because each component has different specific gravity, particle size, and fluidity. is difficult to obtain with good reproducibility. In addition, if the dispersion is non-uniform, there is also the problem that even if the amount of carbon black or the like mixed in is increased, the volume resistivity cannot be reduced accordingly.
従来、カーボンブラックまたはカーボンブラックとグラ
ファイトを高分子溶液に均一に分散させる方法としては
、導電材と高分子材料を予め２本ロール、ミキサーなど
で十分に混合したものを有機溶剤に混合して塗料にする
方法、または導電材混練して塗料にする方法がとられて
いる。Conventionally, the method of uniformly dispersing carbon black or carbon black and graphite in a polymer solution is to mix the conductive material and polymer material thoroughly in advance using two rolls or a mixer, and then mix the mixture with an organic solvent to create a paint. The method used is to mix the conductive material and make it into a paint.
しかし、前者の方法ではカーボンブラックと高分子の粉
末粒度が著しく異なるため、塗膜として均質なものがで
きす、体積抵抗率も大きく、再現性も悪い。これらを解
決するために機械的手段で強力に混合すると導電性カー
ボンのストラフチャーが切断され、均一分散はできても
体積抵抗率は小さくならない。However, in the former method, the particle size of the carbon black and polymer particles are significantly different, resulting in a homogeneous coating film, high volume resistivity, and poor reproducibility. In order to solve these problems, if the conductive carbon is strongly mixed by mechanical means, the stractures of the conductive carbon will be cut, and although uniform dispersion can be achieved, the volume resistivity will not be reduced.
一方、後者の方法では混線中粘度が高くなり均一な混練
物が得にくくなるため、溶液濃度を下げたり、導電材の
混入量を少な（して粘度を下けて行われるので体積抵抗
率が大きい塗料しか得られない。On the other hand, in the latter method, the viscosity increases during mixing, making it difficult to obtain a homogeneous kneaded product, so the volume resistivity is You can only get big paint.
本発明者らは、多量のカーボンブラックまたは分散させ
た溶剤型導電性塗料を得るため、鋭意研究を重ねた結果
、予め導電材を有機溶剤中にボールミルなどにより均一
分散させた分散液と有機溶剤に溶解させた高分子材料を
混合することによって目的を達成しうることを見い出し
、本発明を完成するに至った。In order to obtain a large amount of carbon black or a dispersed solvent-based conductive paint, the inventors of the present invention have conducted intensive research and found that a dispersion in which a conductive material is uniformly dispersed in an organic solvent using a ball mill or the like and an organic solvent. The present inventors have discovered that the object can be achieved by mixing a polymeric material dissolved in a polymer material, and have completed the present invention.
すなわち、本発明の要旨は、
ｆａ）カーボンブラックまたはカーボンブラックとグラ
ファイトの有機溶剤分散物、および（ｂ）有機溶剤に溶
解しうる高分子材料の有機溶剤溶液の混合物であって、
ｆａ）または（１））のいずれよりも高い粘度を有する
ことを特徴とする導電性塗料組成物に存する。That is, the gist of the present invention is: fa) an organic solvent dispersion of carbon black or carbon black and graphite; and (b) a mixture of an organic solvent solution of a polymeric material soluble in the organic solvent,
A conductive coating composition characterized by having a higher viscosity than either fa) or (1)).
導電性カーボンブラックは、比表面積が大きく、吸油性
か大きいため、高分子溶液と混練すると著しく粘度か上
昇し、均一な分散体を得ることはできないが、本発明に
従えば、導電材を有機溶剤中で５〜１５重口％濃度で混
練することによって低粘度（通常約１００〜５（１００
ｃｐ）の均一な分散液か得られ、この分散液を低粘度（
通常約１０００〜５０００ ＣＰ）の高分子溶液と攪拌
混合することは容易で、しかも均一に導電材が分散した
導電性塗料か得られるのである。更に攪拌を継続すると
粘度か徐々に上昇し、分散液（哨および溶液ｔｂ＋のい
ずれの粘度よりも粘度の高い（通常約５０００〜１００
０００ ＣＰ）塗料組成物ができる。この組成物は分散
安定性が良いうえ、体積抵抗率も著しく小さくなる。本
発明によれば、導電材を非常に高い割合で混入すること
ができ、たとえは高分子１００重量部に対して導電材を
１０〜２０ＯｉＪｉｆｔ部加えても容易に均一な混合物
を得ることかできる。Conductive carbon black has a large specific surface area and high oil absorption, so when kneaded with a polymer solution, the viscosity increases significantly and a uniform dispersion cannot be obtained. However, according to the present invention, the conductive material can be By kneading in a solvent at a concentration of 5-15% by weight, a low viscosity (usually about 100-5% (100%
A homogeneous dispersion of cp) was obtained, and this dispersion was mixed with a low viscosity (
It is easy to stir and mix with a polymer solution (usually about 1,000 to 5,000 CP), and it is possible to obtain a conductive paint in which the conductive material is uniformly dispersed. If the stirring is continued, the viscosity will gradually increase, and the viscosity will be higher than that of either the dispersion liquid (Tb+) or the solution tb+ (usually about 5000 to 100%).
000 CP) paint composition is made. This composition has good dispersion stability and also has a significantly low volume resistivity. According to the present invention, the conductive material can be mixed in a very high proportion, and even if 10 to 20 parts of the conductive material are added to 100 parts by weight of the polymer, a uniform mixture can be easily obtained. .
導電材であるカーボンブラックとしては、１）１３Ｐ吸
油量１００〜４００−／１００ｇ、平均粒径ｌＯ〜７０
ｍμのものが好ましく用いられる。Carbon black, which is a conductive material, has 1) 13P oil absorption of 100 to 400-/100g, average particle size of lO to 70;
mμ is preferably used.
グラファイトとしては、結晶性で、粒径数μ〜数百μの
天然または人造グラファイトが用いられる。As the graphite, crystalline natural or artificial graphite having a particle size of several microns to several hundred microns is used.
導電材は、全組成物重量に対し１０〜６０重鉦％の割合
で加える。The conductive material is added at a rate of 10 to 60% by weight based on the total weight of the composition.
カーボンブラックとグラファイトを混合物として用いる
場合、カーボンブラック／グラファイトの重量比は、目
的とする塗膜の導電性を高（するために組成物中のカー
ボンブラックとグラファイトの合計社に応して下表のよ
うに変えて用いる。When carbon black and graphite are used as a mixture, the weight ratio of carbon black/graphite is determined according to the total amount of carbon black and graphite in the composition in order to increase the desired electrical conductivity of the coating film. Change it and use it like this.
第 １ 表
高分子材料としては、フッ素ゴム、ウレタンゴム、ビニ
リデンフルオライド／テトラフルオロエチレン共重合体
が好ましく例示でき、就中フッ素ゴムが特に好ましい。Table 1 Preferred examples of the polymeric material include fluororubber, urethane rubber, and vinylidene fluoride/tetrafluoroethylene copolymer, with fluororubber being particularly preferred.
本発明で用いるフッ素ゴムは高度にフッ素化された弾性
状の共重合体であって、と（に好ましいフッ素コムとし
ては通常４０〜８５モル％のビニリデンフルオライドと
これと共重合しうる少くとも一種の他のフッ素含有エチ
レン性不飽和単量体との弾性状共重合体が挙げられる。The fluororubber used in the present invention is a highly fluorinated elastic copolymer, and the preferred fluorocomb is usually 40 to 85 mol% of vinylidene fluoride and at least one copolymerizable copolymer therewith. Mention may be made of elastomeric copolymers with one other fluorine-containing ethylenically unsaturated monomer.
またフッ素コムとしてポリマー鎖にヨウ素を含むフッ素
ゴム、例えはポリマー鎖末端に０．００１〜１０車組％
、好ましくは０．０１〜５重量％のヨウ素を結合し、前
記と同じ４０〜８５モル％のビニリデンフルオライドと
これと共重合しうる少くとも一種の他のフッ素含有エチ
レン性不飽和単量体とからなる弾性状共重合体を主組成
とするフッ素ゴム（特開昭５２−４０５４３号参照）も
また有効（こ使用することができる。ここにビニリデン
フルオライドと共重合して弾性状共重合体を与える他の
フッ素含有エチレン性不飽和単量体としてはへキサフル
オロプロピレン、ペンタフルオロプロピレン、トリフル
オロエチレン、トリフルオロクロロエチレン、テトラフ
ルオロエチレン、ビニルフルオライド、パーフルオロ（
メチルビニルエーテル）、パーフルオロ（エチルビニル
エーテル）、パーフルオロ（プロピルビニルエーテル）
などが代表的なものとして例示される。とくに望ましい
フッ素？゛ムはビニリデンフルオライド／ヘキサフルオ
ロプロピレン二元弾性状共重合体およびビニリデンフル
オライド／テトラフルオロエチレン／ヘキサフルオロプ
ロピレン三元弾性状共重合体である。In addition, fluorine rubber containing iodine in the polymer chain as a fluorine comb, for example, 0.001 to 10% fluorine rubber at the end of the polymer chain.
, preferably 0.01 to 5% by weight of iodine, and at least one other fluorine-containing ethylenically unsaturated monomer that can be copolymerized with the same 40 to 85 mol% of vinylidene fluoride as described above. Fluororubber (see JP-A-52-40543) whose main composition is an elastic copolymer consisting of Other fluorine-containing ethylenically unsaturated monomers that provide coalescence include hexafluoropropylene, pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoro(
methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether)
etc. are exemplified as representative examples. Is fluorine particularly desirable? The polymers are a vinylidene fluoride/hexafluoropropylene dielastic copolymer and a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene ternary elastic copolymer.
有機溶剤としては、メタノール、エタノール、プロパツ
ール、エチレングリコール、カルピトール、セロソルブ
などのアルコール、メチルエチルケトン、メチルイソブ
チルケトンなどのケトン類が用いられる。また、導電材
の混練用としては、これらのほかに、挿接速度などを調
整するために他の溶剤、たとえばイソホロン、トルエン
、キシレンなどを用いることができる。As the organic solvent, alcohols such as methanol, ethanol, propatool, ethylene glycol, calpitol, and cellosolve, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are used. In addition to these, other solvents such as isophorone, toluene, xylene, etc. can be used for kneading the conductive material in order to adjust the insertion speed and the like.
本発明の組成物には、上記成分の他に、所望により界面
活性剤、加硫剤、受酸剤、充填剤などを加えることかで
きる。In addition to the above-mentioned components, the composition of the present invention may optionally contain a surfactant, a vulcanizing agent, an acid acceptor, a filler, and the like.
界面活性剤は、主として導電材を溶媒中で混練する際に
用いられ、均一分散を促進する。また、脂肪酸エステル
を用いても同様の効果が得られる。A surfactant is mainly used when kneading a conductive material in a solvent, and promotes uniform dispersion. Similar effects can also be obtained by using fatty acid esters.
界面活性剤としては、いずれの界面活性剤も用いること
ができる。界面活性剤の具体例としては、非イオン性界
面活性剤としてソルビタンモノオレエート、アルキルア
ルキロールアミドなト、陰イオン性界面活性剤としてラ
ウリルアルコール硫酸エステルナトリウム塩、陽イオン
性界面活性剤としてオキシエチレンドデシルアミンなと
、その他高級脂肪酸エステルも均一分散に効果的である
。Any surfactant can be used as the surfactant. Specific examples of surfactants include sorbitan monooleate and alkyl alkylolamides as nonionic surfactants, lauryl alcohol sulfate sodium salt as anionic surfactants, and oxychloride as cationic surfactants. Ethylenedodecylamine and other higher fatty acid esters are also effective for uniform dispersion.
界面活性剤は、導電材に対して１〜３０市量部、好まし
くは４〜１５重置部の割合で用いられる。The surfactant is used in a ratio of 1 to 30 parts by weight, preferably 4 to 15 parts by weight, based on the conductive material.
加硫剤としては、アミノシラン化合物またはこれとアミ
ン化合物の混合物か用いられる。As the vulcanizing agent, an aminosilane compound or a mixture of this and an amine compound is used.
アミノシラン化合物としては、γ−アミノプロピルトリ
エトキシシラン（以下、Ａ−１１００と言う）、Ｎ−β
−アミノエチル−γ−アミノプロピルトリメトキシシラ
ン、Ｎ−（トリメトキンンリルプロピル）エチレンジア
ミン、Ｎ−β−アミノエチル−γ−アミノプロピルメチ
ルジメトキンシラン、γ−ウレイドプロピルトリエトキ
シシラン、β−アミノエチル−β−アミノエチル−γ−
アミノプロピルトリメトキシシランなどが挙けられる。Examples of aminosilane compounds include γ-aminopropyltriethoxysilane (hereinafter referred to as A-1100), N-β
-Aminoethyl-γ-aminopropyltrimethoxysilane, N-(trimethinrylpropyl)ethylenediamine, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, β-aminoethyl -β-Aminoethyl-γ-
Examples include aminopropyltrimethoxysilane.
アミン化合物としては、脂肪族炭化水素基に直結する少
なくとも１個の末端アミン基を有するアミン化合物か好
ましく、その代表的な化合物を例示するとエチルアミン
、プロピルアミン、ブチルアミン、ベンジルアミン、ア
リルアミン、ｎ−アミルアミン、エタノールアミンなど
のモノアミン類、エチレンジアミン、トリメチレンジア
ミン、テトラメチレンジアミン、ヘキサメチレンジアミ
ン、３，９−ビス（３−アミノプロピル）−２，４゜８
、ｌＯ−テトラオキサスピロ［５，５）ウンデカン（以
下ｖ−１１という）などのジアミン類、ジエチレントリ
アミン、トリエチレンテトラミン、テトラエチレンペン
タミン、ペンタエチレンヘキサミンなどのポリアミン類
が挙けられ、就中、２個以上の末端アミン基を有するア
ミン化合物がより好ましい。The amine compound is preferably an amine compound having at least one terminal amine group directly connected to an aliphatic hydrocarbon group, and representative examples thereof include ethylamine, propylamine, butylamine, benzylamine, allylamine, and n-amylamine. , monoamines such as ethanolamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 3,9-bis(3-aminopropyl)-2,4゜8
, diamines such as 1O-tetraoxaspiro[5,5)undecane (hereinafter referred to as v-11), polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine, among others, More preferred are amine compounds having two or more terminal amine groups.
アミノシラン化合物の添加量は、通常フッ素ゴム１００
重量部当たり１〜３０重量部、好ましくは１〜２０重量
部である。所望によりアミン化合物を添加した場合には
、アミノシラン化合物とアミン化合物の総和が上記の値
をとる様に配合する。The amount of aminosilane compound added is usually 100% of the fluororubber.
The amount is 1 to 30 parts by weight, preferably 1 to 20 parts by weight. When an amine compound is added as desired, it is blended so that the total sum of the aminosilane compound and the amine compound takes the above value.
割合はモル比で１＝９９〜９０：１０の範囲から選ばれ
る。The ratio is selected from the range of 1=99 to 90:10 in terms of molar ratio.
前記受酸剤としてはフッ素ゴムの加硫に通常用いられる
ものが同様に使用され、例えば２価金属の酸化物または
水酸化物の１種または２種以上か用いられる。具体的に
はマグネシウム、カルシウム、亜鉛、鉛などの酸化物ま
たは水酸化物が例示される。また前記充填剤としてはシ
リカ、クレー、珪藻土、タルク、カーボンなどが用いら
れる。As the acid acceptor, those commonly used in the vulcanization of fluororubber can be similarly used, and for example, one or more of divalent metal oxides or hydroxides can be used. Specific examples include oxides or hydroxides of magnesium, calcium, zinc, lead, and the like. Further, as the filler, silica, clay, diatomaceous earth, talc, carbon, etc. are used.
本発明の塗料組成物は、塗料の通常の塗装法（ハケ塗り
、浸漬、吹付けなど）によって基材に塗布または含浸さ
れ、室温〜４００°Ｃ好ましくは１００〜４００℃の温
度条件下で乾燥、硬化させることによって目的とするフ
ッ素ゴム塗膜とすることができる。The coating composition of the present invention is applied or impregnated onto a substrate by a conventional coating method (brushing, dipping, spraying, etc.) and dried at a temperature of room temperature to 400°C, preferably 100 to 400°C. By curing, the desired fluororubber coating can be obtained.
次に実施例および比較例を示し本発明を具体的に説明す
る。Next, the present invention will be specifically explained with reference to Examples and Comparative Examples.
実施例１
導電材としてアセチレンブラックとグラファイト粉末の
混合物（重量比７：３）１００ｇ、酸化マグネシウム５
ｇ、メチルイソブチルケトン３９５ｇおよびＶ−１１３
，！ｉ＋をボールミルで１４時間混練して分散物を調製
した。粘度６３０ ＣＰ。Example 1 As a conductive material, 100 g of a mixture of acetylene black and graphite powder (weight ratio 7:3), 5 g of magnesium oxide
g, 395 g of methyl isobutyl ketone and V-113
，! i+ was kneaded in a ball mill for 14 hours to prepare a dispersion. Viscosity 630 CP.
一方、ビニリデンフルオライド／ヘキサフルオロプロピ
レン／テトラフルオロエチレン共重合体ゴム（ダイキン
工業株式会社製［ダイエルＧ５０１Ｊ）１５０ｇをメチ
ルエチルケトン５００ｙに溶解して溶液を調製した。粘
度２５００ ＣＰ−０得られた分散物と溶液を高速攪拌
混合すると、徐々に粘度か上昇し、６００００ Ｃｐで
一定となった。これをドクターナイフでポリエステルフ
ィルム上に塗布し、１６０℃で３０分間乾燥して厚さ約
２５μの導電性フィルムを得た。このフィルムの体積抵
抗率は０．０６０Ω・αであった。On the other hand, a solution was prepared by dissolving 150 g of vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymer rubber (manufactured by Daikin Industries, Ltd. [DAIEL G501J) in 500 y of methyl ethyl ketone. Viscosity 2500 CP-0 When the obtained dispersion and solution were mixed with high speed stirring, the viscosity gradually increased and became constant at 60000 Cp. This was applied onto a polyester film using a doctor knife and dried at 160° C. for 30 minutes to obtain a conductive film with a thickness of about 25 μm. The volume resistivity of this film was 0.060Ω·α.
実施例２
実施例１と同じ導電材混合物１００ｇをメチルエチルケ
トン４００．９と共に実施例１と同様に混練して分散物
を調製した。粘度５８０ ＣＰ。Example 2 100 g of the same conductive material mixture as in Example 1 was kneaded with 400.9 g of methyl ethyl ketone in the same manner as in Example 1 to prepare a dispersion. Viscosity 580 CP.
ウレタンゴム（大日本インキ株式会社製「パンデツクス
−５１６７４）１００ｇをジメチルアセトアミド４００
ｇに溶解して溶液を調製した。粘度２８００ｃｐ。100 g of urethane rubber (“Pandex-51674” manufactured by Dainippon Ink Co., Ltd.) was mixed with 400 g of dimethylacetamide.
A solution was prepared by dissolving in g. Viscosity 2800cp.
得られた分散物および溶液を高速攪拌混合して粘度４５
０００ＣＰ の塗料を得た。これから実施例１と同様に
して厚さ約２６μの導電性フィルムを得た。このフィル
ムの体積抵抗率は０．０６８Ω・ａであった。The obtained dispersion and solution were mixed with high speed stirring until the viscosity was 45.
A paint of 000CP was obtained. From this, a conductive film having a thickness of about 26 μm was obtained in the same manner as in Example 1. The volume resistivity of this film was 0.068Ω·a.
比較例１
実施例１で用いた各成分を最初から同時にボールミルで
１８時間混練した。粘度は４５ ｏ ｏ ＯＣＰとなっ
た。これは分散が均一でなく、得られたフィルムの体積
抵抗率は０．４４Ω・０であった。Comparative Example 1 The components used in Example 1 were simultaneously kneaded in a ball mill for 18 hours from the beginning. The viscosity was 45 o OCP. The dispersion was not uniform, and the volume resistivity of the obtained film was 0.44Ω·0.
比較例２
実施例１で用いた各成分を、溶剤を除いて２本ロールで
混練し、これを該溶剤に分散させて分散液を調製した。Comparative Example 2 The components used in Example 1 were kneaded using two rolls except for the solvent, and then dispersed in the solvent to prepare a dispersion.
この分散液から実施例１と同様にしてフィルムを作成し
た。このフィルムの体積抵抗率は０．３２Ω・Ｃであっ
た。A film was prepared from this dispersion in the same manner as in Example 1. The volume resistivity of this film was 0.32Ω·C.
実施例３
導電材としてファーネスブラックとグラファイトの混合
物（重量比４：６）１５０ｇ、酸化マグネンウム５ｇお
よびメチルエチルケトン９９５ｇをボールミルで１３時
間混練して分散物を調製した。粘度１５０ ＣＰ。Example 3 A dispersion was prepared by kneading 150 g of a mixture of furnace black and graphite (weight ratio 4:6) as a conductive material, 5 g of magnesium oxide, and 995 g of methyl ethyl ketone in a ball mill for 13 hours. Viscosity 150 CP.
フッ素ゴム（ダイキン工業株式会社製［ダイエルＧ−９
０１Ｊ ）１００ ｇをメチルエチルケトン３００ｇに
溶解して溶液を調製した。粘度４５００ｃｐ・
得られた分散物と溶液を実施例１と同様に混合して塗料
を得た。この塗料の粘度はｓ ｏ ｏ ｏ ｏｃｐであ
り、これにｖ−１１／メチルエチルケトン（重量比１／
１）６ｇを添加し、フィルム化したものの体積抵抗率は
０．．０２Ω・Ｃであった。Fluororubber (manufactured by Daikin Industries, Ltd. [Dai-el G-9
01J) was dissolved in 300 g of methyl ethyl ketone to prepare a solution. Viscosity: 4500 cp The obtained dispersion and solution were mixed in the same manner as in Example 1 to obtain a paint. The viscosity of this paint is s o o o ocp, and V-11/methyl ethyl ketone (weight ratio 1/
1) The volume resistivity of the film made by adding 6g is 0. ．． It was 02Ω・C.
この組成は、フッ素ゴム１００重量部に対して導電材混
合物が１５０重量部という高割合であるにもかかわらず
、均一に分散した塗料であった。Although this composition had a high ratio of 150 parts by weight of the conductive material mixture to 100 parts by weight of fluororubber, the paint was uniformly dispersed.
特許出願人 ダイキン工業株式会社
代理 人 弁理士青 山 葆（ほか２名）１、事件の表
示
昭和５７年特許願第１３９６０号
２、発明の名称
導電性塗料組成物
３、補正をする者
事件との関゛係 特許出願人
住所 大阪府大阪市北区梅田１丁目１２番３９号新阪急
ビル
名称 （２８５） ダイキン工業株式会社代表者 山
１） 稔
４、代理人 〒５４１
５、補正命令の日付： （ｉ発）
６、補正の対象
７、補正の内容
明細書の発明の詳細な説明の欄中、次の箇所を補正しま
す。Patent applicant: Daikin Industries, Ltd. Agent: Patent attorney Aoyama Aoyama (and 2 others) 1. Indication of the case: Patent Application No. 13960 filed in 1982. 2. Name of the invention: Conductive coating composition 3. Person making the amendment: Related parties Patent applicant address New Hankyu Building 1-12-39 Umeda, Kita-ku, Osaka-shi, Osaka Name (285) Daikin Industries, Ltd. Representative Yama 1) Minoru 4, Agent 541-5, Date of amendment order : (I) 6. Subject of amendment 7. The following sections in the detailed description of the invention in the statement of contents of the amendment will be amended.
（１）５頁末５行、［５０旧）ｃｐＪの後に、「、好ま
しくは約１０ ＋：＋〜２０ ＋ｌ ｌ） ｃｐＪを挿
入。(1) At the end of page 5, line 5, after [50 old) cpJ, insert ", preferably about 10 +: + ~ 20 +l l) cpJ."
（２）５頁末３行、Ｉ’ ５００１’、） ｃｐｌの後
に、［、好ましくは約１ （’１００〜３ （：） （
’、） （’ｌ ｃｐ Ｊを挿入。(2) 3 lines at the end of page 5, I'5001', ) After cpl, [, preferably about 1 ('100-3 (:) (
', ) ('l cp J inserted.
（３）６百３行、ｒｃｐＪの後に、「、好ましくは約６
０００〜２（）旧）（ｌｃｐＪを挿入。(3) On line 603, after rcpJ, ", preferably about 6
000-2 () old) (insert lcpJ.
（４）ｌＯ＠ｄ〜９行、［これとアミン化合物４を、［
アミン化合物もしくはこれら」と訂正。(4) lO@d~9th line, [This and amine compound 4, [
Amine compounds or these” was corrected.
（５Ｎ２頁１０行、し、カーボン１を削除。(Page 5N2, line 10, and carbon 1 is deleted.
以上that's all
Claims (1)
グラファイトの有機溶剤分散物、およびｆｂ）有機溶剤
に溶解しうる高分子材料の有機溶剤溶液の混合物であっ
て、ｆａ）または（ｂ）のいずれよりも高い粘度を有す
ることを特徴とする導電性塗料組成物。 ２、分散液ｆａ）中のカーボンブラックまたはカーボン
ブラックとグラファイトの濃度が５〜１５重量％であり
、分散液の粘度が１００〜５ｏ ｏ ｏ ｃｐである特
許請求の範囲第１４記載の組成物。 ３、カーボンブラックが導電性のアセチレンブラック、
ファーネスブラック、チャンネルブラックまたはサーマ
ルブラックである特許請求の範囲第１項または第２項記
載の組成物。 ４、溶液（ｂ）の高分子材料濃度が１０〜３０重量％で
あり、溶液の粘度が１０００〜５０００ Ｃｐである特
許請求の範囲第１項記載の組成物。 ５、高分子材料がフッ素ゴム、ウレタンゴムまたはフッ
化ビニリデン／テトラフルオロエチレン共重合体である
特許請求の範囲第１唄または第４項記載の組成物。 ６、混合物の粘度が５０００ ＣＰ より高く、かつｌ
ｏ ｏ ｏ ｏ ｏ ｃｐ以下である特許請求の範囲第
１唄記載の組成物。 ７、高分子材料１００重量部に対しカーボンブラックま
たはカーボンブラックとグラファイト１０〜１５０重量
部を含有する特許請求の範囲第１項記載の組成物。 ８、組成物から得たフィルムの体積抵抗率か０．３〜０
．０１Ω・Ｃである特許請求の範囲第１唄記載の組成物
。 ９、混合物中の固形分含有量が１０〜４０重置％である
特許請求の範囲第１項記載の組成物。[Claims] 1. A mixture of fa) carbon black or an organic solvent dispersion of carbon black and graphite, and fb) an organic solvent solution of a polymeric material soluble in the organic solvent, comprising fa) or (b) ) A conductive coating composition characterized by having a higher viscosity than either of the above. 2. The composition according to claim 14, wherein the concentration of carbon black or carbon black and graphite in the dispersion fa) is 5 to 15% by weight, and the viscosity of the dispersion is 100 to 5 o o cp. 3. Carbon black is conductive acetylene black,
3. The composition according to claim 1 or 2, which is furnace black, channel black or thermal black. 4. The composition according to claim 1, wherein the concentration of the polymeric material in the solution (b) is 10 to 30% by weight, and the viscosity of the solution is 1000 to 5000 Cp. 5. The composition according to claim 1 or 4, wherein the polymeric material is fluororubber, urethane rubber, or vinylidene fluoride/tetrafluoroethylene copolymer. 6. The viscosity of the mixture is higher than 5000 CP and l
The composition according to claim 1, which has a cp or less. 7. The composition according to claim 1, which contains 10 to 150 parts by weight of carbon black or carbon black and graphite per 100 parts by weight of the polymeric material. 8. The volume resistivity of the film obtained from the composition is 0.3 to 0.
．． 01Ω·C. 9. The composition according to claim 1, wherein the solid content in the mixture is 10 to 40% by weight.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57013960A JPS58132058A (en) | 1982-01-30 | 1982-01-30 | Electrically conductive paint composition |
| US06/461,598 US4547311A (en) | 1982-01-30 | 1983-01-27 | Electrically conductive coating composition |
| DE8383100814T DE3371220D1 (en) | 1982-01-30 | 1983-01-28 | Electrically conductive coating composition |
| EP83100814A EP0085413B1 (en) | 1982-01-30 | 1983-01-28 | Electrically conductive coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57013960A JPS58132058A (en) | 1982-01-30 | 1982-01-30 | Electrically conductive paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58132058A true JPS58132058A (en) | 1983-08-06 |
| JPS6350383B2 JPS6350383B2 (en) | 1988-10-07 |
Family
ID=11847775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57013960A Granted JPS58132058A (en) | 1982-01-30 | 1982-01-30 | Electrically conductive paint composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4547311A (en) |
| EP (1) | EP0085413B1 (en) |
| JP (1) | JPS58132058A (en) |
| DE (1) | DE3371220D1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6392669A (en) * | 1986-10-08 | 1988-04-23 | Three Bond Co Ltd | Conductive resin composition |
| JPH01166574A (en) * | 1987-12-22 | 1989-06-30 | Fuji Electric Co Ltd | Thin film solar cell |
| JPH0445176A (en) * | 1990-06-11 | 1992-02-14 | Matsushita Electric Ind Co Ltd | Production of coating compound of carbon black |
| JPH04503831A (en) * | 1990-01-31 | 1992-07-09 | アドヒーシブズ・リサーチ・インコーポレイテッド | conductive pressure sensitive adhesive |
| JPH09505352A (en) * | 1994-11-01 | 1997-05-27 | 株式会社ヒューマックステクノロジー | Conductive paint |
| JPH10130567A (en) * | 1996-10-29 | 1998-05-19 | Asahi Glass Kooto & Resin Kk | Coating and coated article |
| JP2010265354A (en) * | 2009-05-13 | 2010-11-25 | Nitta Ind Corp | Method for producing rubber or resin coating material |
| JP2013237783A (en) * | 2012-05-15 | 2013-11-28 | Nippon Zeon Co Ltd | Conductive fluororubber composition |
| JP2015048479A (en) * | 2013-09-04 | 2015-03-16 | ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ | Grafted polymers as oleophobic low adhesion anti-wetting coatings |
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|---|---|---|---|---|
| US4528213A (en) * | 1983-11-22 | 1985-07-09 | Rca Corporation | EMI/RFI Shielding composition |
| JPS6122590A (en) * | 1984-07-10 | 1986-01-31 | ダイキン工業株式会社 | Polymer composite heater |
| US4592961A (en) * | 1984-10-09 | 1986-06-03 | Ercon, Inc. | Particle filled flexible coating composition of aromatic polyester and vinylidene chloride copolymer |
| US4589999A (en) * | 1984-12-28 | 1986-05-20 | E. I. Du Pont De Nemours And Company | Electrically conductive coating composition of a glycidyl acrylic polymer and a reactive polysiloxane |
| EP0197745A1 (en) * | 1985-03-30 | 1986-10-15 | Charles Romaniec | Conductive materials |
| BG41887A1 (en) * | 1985-12-24 | 1987-09-15 | Krstev | Electric resistance matter |
| US4740426A (en) * | 1986-08-29 | 1988-04-26 | E. I. Du Pont De Nemours And Company | Conductive primer composition |
| US4893954A (en) * | 1987-05-13 | 1990-01-16 | Kotur Donald R | Removable keyboard cover for office machines |
| JPH0749560B2 (en) * | 1987-08-07 | 1995-05-31 | ポリプラスチックス株式会社 | Conductive primer or conductive paint for painting plastics |
| EP0311298B1 (en) * | 1987-10-06 | 1996-04-03 | Cabotex Co. Ltd. | Preparing an intercalation compound |
| EP0312077B1 (en) * | 1987-10-16 | 1994-01-26 | E.I. Du Pont De Nemours And Company | Conductive fluoropolymers |
| JPH0260954A (en) * | 1988-08-29 | 1990-03-01 | Daikin Ind Ltd | Antistatic polymeric material |
| US5181006A (en) * | 1988-09-20 | 1993-01-19 | Raychem Corporation | Method of making an electrical device comprising a conductive polymer composition |
| US5093036A (en) * | 1988-09-20 | 1992-03-03 | Raychem Corporation | Conductive polymer composition |
| US5041242A (en) * | 1989-01-12 | 1991-08-20 | Cappar Limited | Conductive coating composition |
| US5200264A (en) * | 1989-09-05 | 1993-04-06 | Advanced Products, Inc. | Thermoset polymer thick film compositions and their use as electrical circuitry |
| US5049313A (en) * | 1989-09-05 | 1991-09-17 | Advanced Products Inc. | Thermoset polymer thick film compositions and their use as electrical circuitry |
| FR2669852B1 (en) * | 1990-11-29 | 1994-07-22 | Inst Textile De France | CONDUCTIVE TAPE AND MANUFACTURING METHOD THEREOF. |
| US5234627A (en) * | 1991-12-11 | 1993-08-10 | Dap, Inc. | Stability conductive emulsions |
| US6171468B1 (en) | 1993-05-17 | 2001-01-09 | Electrochemicals Inc. | Direct metallization process |
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| US6710259B2 (en) | 1993-05-17 | 2004-03-23 | Electrochemicals, Inc. | Printed wiring boards and methods for making them |
| US5476580A (en) * | 1993-05-17 | 1995-12-19 | Electrochemicals Inc. | Processes for preparing a non-conductive substrate for electroplating |
| US6303181B1 (en) | 1993-05-17 | 2001-10-16 | Electrochemicals Inc. | Direct metallization process employing a cationic conditioner and a binder |
| US5725807A (en) * | 1993-05-17 | 1998-03-10 | Electrochemicals Inc. | Carbon containing composition for electroplating |
| JP3037021B2 (en) * | 1993-06-11 | 2000-04-24 | 醇 西脇 | Manufacturing method of conductive resin material |
| US5679277A (en) * | 1995-03-02 | 1997-10-21 | Niibe; Akitoshi | Flame-resistant heating body and method for making same |
| RU2083622C1 (en) * | 1995-08-23 | 1997-07-10 | Товарищество с ограниченной ответственностью "ТИКО" | Conducting varnish-and-dye material |
| RU2083619C1 (en) * | 1995-08-23 | 1997-07-10 | Товарищество с ограниченной ответственностью "ТИКО" | Conducting paint and varnish material |
| RU2083618C1 (en) * | 1995-08-23 | 1997-07-10 | Товарищество с ограниченной ответственностью "ТИКО" | Conducting paint and varnish material |
| US6239223B1 (en) | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
| US5958537A (en) * | 1997-09-25 | 1999-09-28 | Brady Usa, Inc. | Static dissipative label |
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| US7261963B2 (en) * | 2002-11-12 | 2007-08-28 | General Motors Corporation | Corrosion resistant, electrically and thermally conductive coating for multiple applications |
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| US20090311436A1 (en) * | 2006-05-16 | 2009-12-17 | Board Of Trustees Of Michigan State University | Conductive composite materials with graphite coated particles |
| AT505730B1 (en) | 2007-08-16 | 2010-07-15 | Helfenberger Immobilien Llc & | MIXING, ESPECIALLY SPINNING SOLUTION |
| RU2565199C2 (en) * | 2013-07-26 | 2015-10-20 | Общество С Ограниченной Ответственностью "Плазма-Ск" | Method of obtaining of nanostructured carbon coating |
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| JPS5013103A (en) * | 1973-04-24 | 1975-02-12 | ||
| JPS53116496A (en) * | 1977-03-22 | 1978-10-11 | Mitsubishi Gas Chemical Co | Paint for electric resistance body |
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| US3509088A (en) * | 1965-10-22 | 1970-04-28 | Harold R Dalton | Carbon black dispersions,their preparation and film products therewith |
| US3654187A (en) * | 1968-01-30 | 1972-04-04 | Fuji Photo Film Co Ltd | Conductive film for electric heater |
| US3652461A (en) * | 1969-11-10 | 1972-03-28 | Harold R Dalton | Carbon black dispersions their preparation and products therefrom |
| CA960395A (en) * | 1972-09-13 | 1974-12-31 | Piero V. Ronca | Electrically conductive epoxy resin coatings |
| US3993842A (en) * | 1973-04-24 | 1976-11-23 | E. I. Du Pont De Nemours And Company | Electrically conductive elastomeric ink |
| DE2500664C3 (en) * | 1975-01-09 | 1978-08-17 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the production of pigment / plastic concentrates containing carbon black |
| US4265789A (en) * | 1979-10-22 | 1981-05-05 | Polymer Cencentrates, Inc. | Conductive polymer processable as a thermoplastic |
| US4351746A (en) * | 1980-07-25 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Compound dispersions and films |
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- 1982-01-30 JP JP57013960A patent/JPS58132058A/en active Granted
-
1983
- 1983-01-27 US US06/461,598 patent/US4547311A/en not_active Expired - Lifetime
- 1983-01-28 DE DE8383100814T patent/DE3371220D1/en not_active Expired
- 1983-01-28 EP EP83100814A patent/EP0085413B1/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5013103A (en) * | 1973-04-24 | 1975-02-12 | ||
| JPS53116496A (en) * | 1977-03-22 | 1978-10-11 | Mitsubishi Gas Chemical Co | Paint for electric resistance body |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6392669A (en) * | 1986-10-08 | 1988-04-23 | Three Bond Co Ltd | Conductive resin composition |
| JPH01166574A (en) * | 1987-12-22 | 1989-06-30 | Fuji Electric Co Ltd | Thin film solar cell |
| JPH04503831A (en) * | 1990-01-31 | 1992-07-09 | アドヒーシブズ・リサーチ・インコーポレイテッド | conductive pressure sensitive adhesive |
| JPH0445176A (en) * | 1990-06-11 | 1992-02-14 | Matsushita Electric Ind Co Ltd | Production of coating compound of carbon black |
| JPH09505352A (en) * | 1994-11-01 | 1997-05-27 | 株式会社ヒューマックステクノロジー | Conductive paint |
| JPH10130567A (en) * | 1996-10-29 | 1998-05-19 | Asahi Glass Kooto & Resin Kk | Coating and coated article |
| JP2010265354A (en) * | 2009-05-13 | 2010-11-25 | Nitta Ind Corp | Method for producing rubber or resin coating material |
| JP2013237783A (en) * | 2012-05-15 | 2013-11-28 | Nippon Zeon Co Ltd | Conductive fluororubber composition |
| JP2015048479A (en) * | 2013-09-04 | 2015-03-16 | ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ | Grafted polymers as oleophobic low adhesion anti-wetting coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3371220D1 (en) | 1987-06-04 |
| EP0085413B1 (en) | 1987-04-29 |
| EP0085413A3 (en) | 1984-04-04 |
| US4547311A (en) | 1985-10-15 |
| JPS6350383B2 (en) | 1988-10-07 |
| EP0085413A2 (en) | 1983-08-10 |
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